Bicyclo(3.3.1)nonanes and bicyclo(3.3.1)nonenes and their use as flavor or fragrance ingredient

ABSTRACT

The present invention relates to substituted bicyclo[3.3.1]nonanes and bicyclo[3.3.1]nonenes of formula (I) 
                         
wherein R, and R 1  to R 5  have the same meaning as described in the specification.

This is an application filed under 35 USC 371 of 35 USC 371 ofPCT/CH2005/000014.

The present invention relates to substitued bicyclo[3.3.1]nonanes andbicyclo[3.3.1]nonenes, having ambery, woody odour notes. This inventionrelates furthermore to a method of their production and to flavour andfragrance compositions comprising them.

In the fragrance industry there is always an ongoing demand for newcompounds that enhance or improve on odour notes, or impart new odournotes.

Surprisingly, we have found a novel class of compounds having muchsought-after ambery woody odour notes and which may be produced fromreadily-available cheap and naturally available starting materials.

In a first aspect the invention refers to a compound of formula (I)

wherein

-   -   R is isopropyl or iso-propenyl;    -   R¹ is hydrogen, methyl or ethyl;    -   R² and R³ are independently hydrogen, methyl, or ethyl; or    -   R² and R³ taken together is ethylidene; or    -   R² and R³ taken together is a divalent radical (CH₂)₂ which        forms cyclopropane together with the carbon atom to which they        are attached;    -   R⁴ and R⁵ are independently hydrogen, hydroxy, C₁ to C₃ alkoxy,        e.g. methoxy, ethoxy, or C₂ to C₃ acyloxy, e.g. acetoxy; or    -   R⁴ and R⁵ together with the carbon atom to which they are        attached form a 1,3-dioxolane ring or a 1,3-dioxane ring; or    -   R⁴ and R⁵ together with the carbon atom to which they are        attached form a carbonyl group;    -   the bond between C2 and C3 is a single bond, or the dotted line        together with the bond between C2 and C3 represents a double        bond; and    -   the bond between C7 and C8 is a single bond, or the dotted line        together with the bond between C7 and C8 represents a double        bond.

The compounds according to the present invention contain several chiralcentres and as such may exist as a mixture of stereoisomers, or they maybe resolved as isomerically pure forms. Resolving stereoisomers adds tothe complexity of manufacture and purification of these compounds and soit is preferred to use the compounds as mixtures of their stereoisomerssimply for economic reasons. However, if it is desired to prepareindividual stereoisomers, this may be achieved according to methodologyknown in the art, e.g. preparative HPLC and GC or by stereoselectivesyntheses.

Particular preferred compounds of formula (I) are5-isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-one;4-ethyl-5-isopropenyl-8-methylbicyclo[3.3.1]non-7-en-2-one;5-isopropenyl-3,4,8-trimethylbicyclo[3.3.1]non-7-en-2-one;5-isopropenyl-3,3,4,8-tetramethylbicyclo[3.3.1]non-7-en-2-one;5-isopropenyl-8,8-dimethoxy-2,6-dimethylbicyclo[3.3.1]non-2-ene;4,8-dimethyl-5-isopropenylspiro[bicyclo[3.3.1]nonane-2,2′-[1,3]dioxolane];5-isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-ol;5-isopropenyl-2,4,8-trimethylbicyclo[3.3.1]non-7-en-2-ol;5-isopropyl-4,8-dimethylbicyclo[3.3.1]nonan-2-one,5-isopropenyl-8-methylbicyclo[3.3.1]non-7-en-2-one,5-isopropenyl-3,4,8-trimethylbicyclo[3.3.1]non-7-en-2-one, and4,8-dimethyl-5-isopropenyl-8-methoxy-bicyclo[3.3.1]non-7-ene.

The compounds according to the present invention may be used alone or incombination with a base material. As used herein, the “base material”includes all known odourant molecules selected from the extensive rangeof natural and synthetic molecules currently available, such asessential oils, alcohols, aldehydes and ketones, ethers and acetals,esters and lactones, macrocycles and heterocycles, and/or in admixturewith one or more ingredients or excipients conventionally used inconjunction with odourants in fragrance compositions, for example,carrier materials, and other auxiliary agents commonly used in the art.

The following list comprises examples of known odourant molecules, whichmay be combined with the compounds of the present invention:

-   -   ethereal oils and extracts, e.g. tree moss absolute, basil oil,        castoreum, costus root oil, myrtle oil, oak moss absolute,        geranium oil, jasmin absolute, patchouli oil, rose oil,        sandalwood oil, wormwood oil, lavender oil or ylang-ylang oil;    -   alkohols, e.g. citronellol, Ebanol™, eugenol, farnesol,        geraniol, Super Muguet™, linalool, phenylethyl alcohol,        Sandalore™, terpineol or Timberol™.    -   aldehydes and ketones, e.g. α-amylcinnamaldehyd, Georgywood™,        hydroxycitronellal, Iso E Super®, Isoraldeine®, Hedione®,        maltol, methyl cedryl ketone, methylionone or vanillin;    -   ether and acetals, e.g. Ambrox™, geranyl methyl ether, rose        oxide or Spirambrene™.    -   esters and lactones, e.g. benzyl acetate, cedryl actetate,        γ-decalactone, Helvetolide®, γ-undecalactone or vetivenyl        acetate.    -   macrocycles, e.g. ambrettolide, ethylene brassylate or        Exaltolide®.    -   heterocycles, e.g. isobutylchinoline.

The compounds of the present invention may be used in a broad range offragrance applications, e.g. in any field of fine and functionalperfumery, such as perfumes, household products, laundry products, bodycare products and cosmetics. The compounds can be employed in widelyvarying amounts, depending upon the specific application and on thenature and quantity of other odourant ingredients. The proportion istypically from 0.001 to 20 weight percent of the application. In oneembodiment, compounds of the present invention may be employed in afabric softener in an amount of from 0.001 to 0.05 weight percent. Inanother embodiment, compounds of the present invention may be used infine perfumery in amounts of from 0.1 to 20 weight percent, morepreferably between 0.1 and 5 weight percent. However, these values aregiven only by way of example, since the experienced perfumer may alsoachieve effects or may create novel accords with lower or higherconcentrations.

The compounds of the present invention may be employed into thefragrance application simply by directly mixing the fragrancecomposition with the fragrance application, or they may, in an earlierstep be entrapped with an entrapment material, for example, polymers,capsules, microcapsules and nanocapsules, liposomes, film formers,absorbents such as carbon or zeolites, cyclic oligosaccharides andmixtures thereof, or they may be chemically bonded to substrates, whichare adapted to release the fragrance molecule upon application of anexternal stimulus such as light, enzyme, or the like, and then mixedwith the application.

Thus, the invention additionally provides a method of manufacturing afragrance application, comprising the incorporation of a compound offormula (I) as a fragrance ingredient, either by directly admixing thecompound of formula (I) to the application or by admixing a fragrancecomposition comprising a compound of formula (I), which may then bemixed to a fragrance application, using conventional techniques andmethods.

As used herein, “fragrance application” means any product, such as fineperfumery, e.g. perfume and Eau de Toilette; household products, e.g.detergents for dishwasher, surface cleaner; laundry products, e.g.softener, bleach, detergent; body care products, e.g. shampoo, showergel; and cosmetics, e.g. deodorant, vanishing creme, comprising anodourant. This list of products is given by way of illustration and isnot to be regarded as being in any way limiting.

Compounds of formula (I) wherein R⁴ and R⁵ together with the carbon atomto which they are attached form a carbonyl group (see formula (II)below) may be prepared by the reaction of α-pinene with α,β-unsaturatedcarboxylic acids or derivatives thereof such as alkenoyl halogenide,e.g. crotonyl chloride, crotonyl bromide and pentenoyl chloride; oralkenoyl anhydride, for example crotonic anhydride, in the presence of acatalytic amount of an acid, such as Lewis acid or Bronsted acid.

Surprisingly we have found that certain compounds of formula (I) mayalso be prepared by reacting α-pinene with β,γ-unsaturated carboxylicacids or β-hydroxy carboxylic acids, resulting in a ketone of formula(II) in the presence of a catalytic amount of an acid. It is believedthat, due to the acidic conditions, both the β,γ-unsaturated carboxylicacids and the β-hydroxy carboxylic acids will transfer to thecorresponding α,β-unsaturated carboxylic acids, which then will reactwith α-pinene.

The resulting compounds of formula (II) may be alkylated to give furthercompounds of formula (I). Still further compounds of formula (I) may beprepared by reduction and/or acylation of the carbonyl group at C2 or byGrignard reaction and acylation of the carbonyl group at C2. Stillfurther compounds of formula (I) may be prepared by hydrogenation.

Compounds of formula (I) wherein either R² or R³ is not hydrogen, and R⁴and R⁵ together with the carbon atom to which they are attached form acarbonyl group may also be prepared by the reaction of α-pinene withα,β-unsaturated α-alkyl carboxylic acids, e.g. 2-methylcrotonylchloride, 2-ethylcrotonyl chloride, 2-methylcrotonic anhydride, in thepresence of a catalytic amount of an acid.

Optionally pure compounds of formula (I) and enantiomer mixtures of acompound of formula (I) enriched in one enantiomer may be synthesized bystarting from the optically pure α-pinene or from an enantiomer mixtureenriched in either (S)-(+)-α-pinene or (R)-(−)-α-pinene respectively.

The invention is now further described with reference to the followingnon-limiting examples.

EXAMPLE 1 5-Isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-one (1)

a) A mixture of 30 g α-pinene ((1S)-(−)/(1R)-(+) 90:10, 0.22 mol), 67.8g crotonic anhydride (0.44 mol, 2 eq.) and 4.95 g zinc bromide (0.021mol, 0.1 eq.) was heated at 95° C. for 7 h. The reaction mixture wasthen treated with 50 ml H₂O and heated 3 h at reflux. Extraction withEt₂O, drying of the org. phases with Na₂SO₄ followed byVigreux-distillation and FC (Flash Chromatography) (SiO₂, hexane/Et₂O95:5) gave 990 mg (2%) of compound 1. The boiling point of the endproduct is 80° C. at 0.07 torr (0.09 mbar).

[α]_(D) ²²=−280.5 (c=0.93, EtOH)

Odour description: woody, resinous, fir, fruity raspberry ketone-like,olibanum-like, ciste, ambery

b) According to the procedure described above starting from (−)-α-pinenein the presence of crotonyl chloride at 90° C. for 4 hours.

[α]_(D) ²²=−785 (c=0.75, EtOH)

Odour description: fruity, woody, piny, ambery

c) According to the procedure describe above starting from (+)-α-pinenein the presence of crotonic anhydride at 95° C. for 6 h.

[α]_(D) ²²=+536.2 (c=1.02, EtOH)

Odour description: grapefruit, red fruit, piny, ambery

¹H-NMR (400 MHz, CDCl₃): δ5.63-5.59 (br. m, H—C(7)), 4.75-4.72 (br. s,H_(r)—CH═), 4.64-4.62 (br. s, H_(c)—CH═), 3.08 (dd, J=6.7, 14.5,H_(α)—C(3)), 2.82-2.78 (br. s, H—C(1)), 2.45-2.31 (m, C(6)H₂), 2.27(quintet t, J=2.0, 7.0, H—C(4)), 2.18 (dd, J=3.3, 12.8, irrad. at2.80→d, J=12.8, H_(syn)—C(9)), 1.89 (dt, J=1.6, 14.5, irrad. at 2.80→dd,J=1.6, 14.0, H_(β)—C(3)), 1.87 (dt, J=2.6, 12.8, irrad. at 2.80→dd,J=2.2, 13.0, H_(anti)—C(9)), 1.73 (s, MeC═CH₂), 1.66 (br. s, J=1.9,MeC(8)), 0.80 (d, J=7.2, MeC(4)).

¹³C-NMR (100 MHz, CDCl₃): δ212.42 (s, CO), 150.75 (s, C(5)C═), 134.36(s, C(8)), 124.85 (d, C(7)), 108.75 (t, CH₂═), 53.98 (d, C(1)), 40.92(t, C(3)), 39.40 (d, C(4)), 39.25 (t, C(6)), 39.17 (s, C(5)), 31.20 (t,C(9)), 21.79 (q, MeC(8)), 18.42 (q, MeC═CH₂), 16.59 (q, MeC(4)).

MS (EI): 204 (34), 189 (8), 171 (4), 161 (11), 147 (19), 134 (30), 133(50), 119 (99), 105 (78), 97 (93), 93 (100), 91 (87), 77 (49), 69 (28),41 (70).

IR: ν_(max) 2954, 2877, 1718, 1659, 1445, 1376, 1311, 1292, 1267, 1181,1101, 1027, 968, 838, 688 cm⁻¹.

EXAMPLE 2 4-Ethyl-5-isopropenyl-8-methylbicyclo[3.3.1]non-7-en-2-one (2)

At 30° C., a mixture of 7.35 g of 2-pentenoyl chloride (62 mmol) and 1.7g of zinc chloride (12 mmol, 0.2 eq.) in 85 ml ethylene chloride wastreated dropwise within 20 min. with a solution of 19.4 g of(−)-alpha-pinene (142 mmol, 2 eq.) in 20 ml ethylene dichloride. Thereaction mixture was then stirred at 30° C. for 30 min., then at 50° C.for 2 h, and finally at 80° C. for 1 h. After cooling, the reactionmixture was washed with aq. sat. NaCl soln. and aq. sat. NaHCO₃ soln.The aq. phases were extracted with Et₂O, dried (Na₂SO₄), andconcentrated. FC (SiO₂, hexane/Et₂O 20:1) of the crude (26 g) gave 1.74g (13%) of compound 2. The boiling point of the end product is 95° C. at0.06 torr (0.08 mbar).

¹H-NMR (400 MHz, CDCl₃): δ5.63-5.60 (tq, J=1.5, 3.5, H—C(7)), 4.63(quintet, J=1.3, H_(r)—CH═), 4.66-4.65 (br. s, H_(c)—CH═), 2.93 (ddd,J=1.6, 6.3, 14.7, H_(α)—C(3)), 2.81-2.78 (br. s, H—C(1)), 2.44-2.30 (m,C(6)H₂), 2.14 (dt, J=1.6, 14.8, H_(β)—C(3)), 2.09 (dd, J=3.4, 12.6,H_(syn)—C(9)), 1.89 (dt, J=2.7, 12.6, H_(anti)—C(9)), 1.88-1.81 (m,H—C(4)), 1.72 (dd, J=0.6, 1.3, MeC═CH₂), 1.67 (td, J=1.5, 2.3, MeC(8)),1.36-1.24 (sext t, J=1.8, 7.7, 13.5, MeCH—C(4)), 1.03-1.09 (dqd, J=6.2,7.3, 13.4, MeCH—C(4)), 0.87 (d, J=7.2, MeCH₂).

¹³C-NMR (100 MHz, CDCl₃): δ212.75 (s, CO), 151.13 (s, C(5)C═), 134.71(s, C(8)), 125.04 (d, C(7)), 109.09 (t, CH₂═), 53.98 (d, C(1)), 47.24(d, C(4)), 40.07 (s, C(5)), 39.52 (t, C(6)), 36.64 (t, C(3)), 32.19 (t,C(9)), 22.48 (t, CH₂Me), 21.97 (q, MeC(8)), 18.76 (q, MeC═CH₂), 12.77(q, MeCH₂).

MS (EI): 219 (5), 218 (28), 203 (5), 190 (4), 189 (14), 175 (9), 162(4), 161 (15), 148 (5), 147 (16), 145 (5), 136 (9), 135 (26), 134 (44),133 (56), 132 (12), 131 (6), 126 (5), 125 (7), 121 (19), 120 (20), 119(100), 117 (17), 115 (15), 112 (5), 111 (68), 108 (12), 107 (26), 106(17), 105 (74), 103 (9), 97 (17), 95 (20), 94 (15), 93 (90), 92 (34), 91(84), 83 (28), 81 (14), 80 (8), 79 (34), 78 (12), 77 (47), 42 (17), 65(20), 55 (39), 53 (21), 51 (10), 41 (55), 39 (28), 29 (13), 27 (11).

IR: ν_(max) 2963, 2928, 2876, 1707, 1678, 1638, 1448, 1379, 1225, 1153,1089, 1062, 1009, 916, 889, 857, 811, 786, 727 cm⁻¹.

[α]_(D) ²²=−572.7 (1.07 in EtOH)

Odour description: ambery, woody, spicy

EXAMPLE 3(1S*3S*4S*5R*)-5-Isopropenyl-3,4,8-trimethylbicyclo[3.3.1]non-7-en-2-one(3)

At 0° C., 15.3 ml of a soln. of LDA (2M in THF/heptane/ethylbenzene, 31mmol, 2.5 eq.) was treated dropwise with a soln. of 2.5 g of5-Isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-one (12 mmol) in 25ml THF. The reaction mixture was stirred 1.5 h at 0° C., treated with2.6 ml methyl iodide (41.7 mmol, 3.4 eq.), stirred at 25° C. for 3 h,and poured into 1M aq. HCl soln. Extraction with MTBE (2×80 ml), washingof the org. phase with H₂O, aq. sat. NaCl soln., drying (MgSO₄) gave 3.6g crude. FC (hexane/MTBE 24:1) gave 0.56 g (21%) of compound 3. Theboiling point of the end product is 120° C. at 0.08 mbar. R_(f)(hexane/MTBE 24:1) 0.26.

¹H-NMR (400 MHz, CDCl₃): δ5.54-5.50 (m, H—C(7)), 4.78 (quintet, J=1.3,H_(t)—CH═), 4.72-4.70 (br. s, H_(c)—CH═), 2.82-2.78 (br. s, H—C(1)),2.35-2.22 (m, C(6)H₂, H_(syn)—C(9), H—C(3)), 1.84 (dq (quintet), J=7.3,H—C(4)), 1.79 (td, J=1.6, 2.3, MeC(8)), 1.72 (dd, J=0.9, 1.6, MeC═CH₂),1.70 (dd, J=2.3, 13.0, H_(anti)—C(9)), 1.20 (d, J=7.5, Me—C(3)), 0.86(d, J=7.2, Me—C(4)).

¹H-NMR (400 MHz, C₆D₆): δ5.24-5.20 (m, H—C(7)), 4.78 (quintet, J=1.4,H_(t)—CH═), 4.63-4.60 (br. s, H_(c)—CH═), 2.71-2.67 (br. s, H—C(1)),2.10-2.03 (m, H_(β)—C(6)), 2.07 (dq (quintet), J=7.5, H—C(3)), 1.91(ddd, J=1.9, 2.8, 13.0, H_(syn)—C(9)), 1.93-1.85 (ddt, J=1.8, 4.6, 13.0,H_(α)—C(6)), 1.76 (td, J=1.6, 2.3, MeC(8)), 1.55 (dq (quintet), J=7.3,H—C(4)), 1.54 (dd, J=0.9, 1.6, MeC═CH₂), 1.35 (dd, J=2.9, 13.0,H_(anti)—C(9)), 1.12 (d, J=7.3, Me—C(3)), 0.69 (d, J=7.2, Me—C(4)).

¹³C-NMR (100 MHz, CDCl₃): δ212.75 (s, CO), 151.01 (s, C(5)C═), 132.72(s, C(8)), 124.48 (d, C(7)), 109.60 (t, CH₂═), 51.98 (d, C(1)), 48.25(br. d, C(3)), 41.15 (br. d, C(4)), 39.35 (t, C(6)), 39.33 (s, C(5)),29.99 (t, C(9)), 21.58 (q), 20.12 (q), 19.50 (br. q), 18.22 (q).

¹³C-NMR (100 MHz, C₆D₆): δ210.1 (s, CO), 151.0 (s, C(5)C═), 133.3 (s,C(8)), 123.9 (d, C(7)), 110.1 (t, CH₂═), 51.8 (d, C(1)), 47.4 (br. d,C(3)), 40.6 (br. d, C(4)), 39.7 (s, C(5)), 39.4 (t, C(6)), 30.2 (t,C(9)), 21.8 (q, Me—C(8)), 20.6 (q), MeC═CH₂), 17.9 (br. q, Me—C(3)),17.6 (q, Me—C(4)).

MS (EI): 218 (27), 203 (8), 190 (8), 185 (3), 175 (8), 161 (11), 147(19), 133 (66), 119 (100), 111 (47), 107 (47), 105 (72), 93 (72), 91(76), 83 (57), 77 (43), 65 (18), 55 (48), 41 (62).

IR: ν_(max) 2969, 2934, 1708, 1636, 1448, 1376, 1233, 1155, 1092, 1061,1040, 994, 955, 919, 890, 814, 781, 734, 649 cm⁻¹.

[α]_(D) ²²=−655.3 (c=0.99, EtOH)

Odour description: woody, green, floral, rosy, ambery

EXAMPLE 4 5-Isopropenyl-3,3,4,8-tetramethylbicyclo[3.3.1]non-7-en-2-one(4)

At 55° C., a mixture of 9.9 g KOH (176 mmol, 15 eq.) in 40 ml DMSO wastreated dropwise with a soln. of 2.4 g of of5-isopropenyl-4,8-dimethyl-bicyclo[3.3.1]non-7-en-2-one (11.7 mmol) in3.7 ml methyliodide (59 mmol, 5 eq.). The reaction mixture was stirred1.5 h at 60° C., treated with 2.0 ml methyl iodide (32 mmol, 2.7 eq.),stirred at 60° C. for 1.5 h, treated with 1.7 ml methyl iodide (27 mmol,2.3 eq.), stirred at 60° C. for 1.5 h, cooled, and poured into 200 ml of2M aq. HCl soln. Extraction with hexane (2×100 ml), washing of the org.phase with H₂O, aq. sat. NaCl soln., drying (MgSO₄) gas 2.6 g crude. FC(hexane/MTBE 15:1) gave 0.7 g (26%) of compound 4. The boiling point ofthe end product is 120° C. at 0.08 mbar. R_(r) (hexane/MTBE 15:1) 0.27.

¹H-NMR (400 MHz, CDCl₃): δ5.55-5.51 (m, H—C(7)), 4.83 (quintet, J=1.4,H_(r)—CH═), 4.75-4.73 (br. s, H_(c)—CH═), 2.86-2.83 (m, H—C(1)),2.43-2.35 (m, H—C(6)), 2.33-2.25 (m, H—C(6)), 2.28 (ddd, J=1.6, 3.0,13.0, H_(anti)—C(9)), 1.96 (qd, J=1.0, 7.4, H—C(4)), 1.80 (dd, J=0.5,1.3, MeC═CH₂), )), 1.70 (dd, J=1.1, 13.0, H_(syn)—C(9)), 1.70 (q, J=1.8,MeC(8)), 1.21 (s, Me), 1.07 (s, Me), 0.85 (d, J=7.5, MeC(4)).

¹³C-NMR (100 MHz, CDCl₃): δ214.58 (s, CO), 151.65 (s, C(5)C═), 133.10(s, C(8)), 124.94 (d, C(7)), 109.91 (t, CH₂═), 52.58 (d, C(1)), 47.15(s, C(3)), 45.15 (d, C(4)), 40.64 (s, C(5)), 40.49 (t, C(6)), 31.33 (q),30.55 (t, C(9)), 25.21 (q), 22.18 (q), 21.44 (q), 13.95 (q).

MS (EI): 218 (27), 203 (8), 190 (8), 185 (3), 175 (8), 161 (11), 147(19), 133 (66), 119 (100), 111 (47), 107 (47), 105 (72), 93 (72), 91(76), 83 (57), 77 (43), 65 (18), 55 (48), 41 (62).

IR: ν_(max) 2969, 2934, 1708, 1636, 1448, 1376, 1233, 1155, 1092, 1061,1040, 994, 955, 919, 890, 814, 781, 734, 649 cm⁻¹.

Odour description: woody, ambery

EXAMPLE 5(1S*4S*5R*)-5-Isopropenyl-8,8-dimethoxy-2,6-dimethylbicyclo[3.3.1]non-2-ene(5)

A soln. of 1.5 g of5-isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-one (7.3 mmol), 1.4 gpara-toluenesulfonic acid mono hydrate (7.4 mmol 1 eq.), and 0.78 gtrimethylorthoformate (7.4 mmol, 1 eq.) in 50 ml methanol was heated at60° C. for 66 h. The reaction mixture was then cooled and poured intoaq. sat. NaHCO₃ soln. (20 ml). Extraction with MTBE (2×80 ml) followedby washing of the aq. phases with H₂O and aq. sat. NaCl soln., drying oforg. phases (MgSO₄) led to 1.8 g of crude product. FC (SiO₂, Hexane/MTBE30:1) gave 1.7 g (92%) of compound 5 as colorless liquid. The boilingpoint of the end product is 130° C. at 0.08 mbar. R_(f) (hexane/MTBE8:1) 0.57.

¹H-NMR (400 MHz, CDCl₃): δ5.48 (tq, J=1.4, 3.7, H—C(7)), 4.63 (quintet,J=1.4, H_(r)—CH═), 4.61-4.60 (br. s, H_(c)—CH═), 3.20 (s, OMe), 3.17 (s,OMe), 2.49-2.45 (m, irrad. at 1.43→changes, H—C(1)), 2.17-2.02 (m,C(6)H₂), 1.97 (dd, J=3.0, 12.4, irrad. at 1.43→br. d, J≈4.0,H_(syn)—C(9)), 1.88 (dd, J≈6.2, 14.4, H_(α)—C(3)), 1.90-1.81 (m, irrad.at 1.43→changes, H—C(4)), 1.79 (td, J=1.7, 2.1, MeC(8)), 1.66 (dd,J=0.6, 1.4, MeC═CH₂), 1.69-1.61 (m, irrad. at 2.47→changes, H_(β)—C(3)),1.43 (ddd, J=1.6, 3.5, 12.5, irrad. at 2.47→dd, J=1.4, 12.6,H_(anti)—C(9)), 0.88 (d, J=7.7, MeC(4)).

¹H-NMR (400 MHz, C₆D₆): δ5.49-5.45 (m, H—C(7)), 4.77-4.73 (m, CH₂═),3.05 (s, OMe), 3.03 (s, OMe), 2.49-2.44 (m, H—C(1)), 2.12-2.05 (m,H—C(6)), 2.05 (dd, J=2.8, 12.3, H_(syn)—C(9)), 1.96 (td, J=1.7, 2.1,MeC(8)), 1.99-1.91 (m, H—C(6)), 1.93 (dd, J=6.2, 13.5, H_(α)—C(3)), 1.71(quintet t, J=1.7, 7.2, H—C(4)), 1.63 (dt, J=1.9, 13.5, H_(β)—C(3)),1.61 (dd, J=0.6, 1.2, MeC═CH₂), 1.48 (ddd, J=1.8, 3.5, 12.4,H_(anti)—C(9)), 1.06 (d, J=7.3, MeC(4)).

¹³C-NMR (100 MHz, CDCl₃): δ152.59 (s, C(5)C═), 135.79 (s, C(8)), 124.07(d, C(7)), 107.32 (t, CH₂═), 102.98 (s, C(2)), 47.59 (q, OMe), 47.47 (q,OMe), 40.59 (d), 40.14 (t, C(6)), 39.12 (s, C(5)), 37.05 (d), 32.53 (t,C(9)), 27.90 (t, C(3)), 24.45 (q), 18.33 (q), 17.41 (q).

¹³C-NMR (100 MHz, C₆D₆): δ152.71 (s, C(5)C═), 136.37 (s, C(8)), 124.13(d, C(7)), 107.78 (t, CH₂═), 103.25 (s, C(2)), 47.46 (q, OMe), 46.38 (q,OMe), 40.90 (d), 40.61 (t, C(6)), 39.65 (s, C(5)), 37.47 (d), 33.36 (t,C(9)), 27.30 (t, C(3)), 24.97 (q), 18.57 (q), 18.02 (q).

MS (EI): 250 (0.2), 218 (31), 203 (19), 187 (5), 171 (12), 137 (57), 115(100), 91 (35), 77 (23), 69 (15), 55 (16), 41 (35).

IR: ν_(max) 2945, 2829, 1638, 1451, 1366, 1308, 1194, 1160, 1130, 1110,1086, 1051, 1018, 972, 953, 922, 886, 846, 799, 772 cm⁻¹.

[α]_(D) ²² =−150.1 (c=1.00, EtOH)

Odour description: ambery, woody, fruity, sweet

EXAMPLE 6(1S*4S*5R*)-4,8-Dimethyl-5-isopropenylspiro[bicyclo[3.3.1]nonane-2,2′-[1,3]dioxolane](6)

A soln. of 2.0 g of5-isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-one (9.8 mmol) in 100ml cyclohexane was treated with 1.8 g ethyleneglycol (2.9 mmol, 3.0 eq.)and 0.2 g para-toluenesulfonic acid mono hydrate (1.0 mmol 0.1 eq.). Thesoln. obtained was heated at reflux for 3 h (Dean-Stark apparatus),cooled and poured into aq. sat. NaHCO₃ soln. (100 ml). Extraction withMTBE (2×80 ml) followed by washing of the aq. phases with H₂O (100 ml)and aq. sat. NaCl soln. (150 ml), drying of org. phases over MgSO₄ ledto 2.6 g of crude product. FC (SiO₂, hexane/MTBE 19:1) gave 0.76 g (31%)of compound 6 as colorless liquid. The boiling point of the end productis 130° C. at 0.09 mbar. R_(f) (hexane/MTBE 19:1) 0.47.

¹H-NMR (400 MHz, CDCl₃): δ5.49 (tq, J=1.4, 3.5, H—C(7)), 4.64 (quintet,J=1.4, H_(t)—CH═), 4.62-4.60 (br. s, H_(c)—CH═), 4.03-3.88 (m,OCH₂CH₂O), 2.21-2.18 (br. s, H—C(1)), 2.17 (dd, J=6.2, 13.8,H_(α)—C(3)), 2.14-2.09 (m, C(6)H₂), 2.09 (dd, J=2.9, 12.9,H_(syn)—C(9)), 1.92 (quintet t, J=1.7, 7.2, H—C(4)), 1.79 (td, J=1.5,2.2, MeC(8) ), 1.66 (dd, J=0.6, 1.3, MeC═CH₂), 1.52 (ddd, J=1.9, 3.4,12.6, H_(anti)—C(9)), 1.36 (dt, J=1.8, 13.9, H_(β)—C(3)), 0.89 (d,J=7.2, MeC(4)).

^(—)C-NMR (100 MHz, CDCl₃): δ152.43 (s, C(5)C═), 135.84 (s, C(8)),123.96 (d, C(7)), 111.52 (s, C(2)), 107.53 (t, CH₂═), 64.27 (t, OCH₂),63.46 (t, OCH₂), 43.56 (d), 39.89 (t, C(6)), 38.92 (s, C(5)), 37.34 (d),34.16 (t, C(9)), 28.70 (t, C(3)), 23.97 (q), 18.32 (q), 16.88 (q).

MS (EI): 248 (1), 233 (0.2), 203 (0.3), 147 (2), 133 (3), 119 (5), 113(100), 105 (6), 91 (9), 86 (4), 77 (5), 69 (9), 41 (9).

IR: ν_(max) 2962, 2885, 1638, 1450, 1368, 1308, 1162, 1129, 1110, 1083,1063, 1042, 1020, 975, 953, 925, 887, 845, 831, 801 cm⁻¹.

[α]_(D) ²²=−142.8 (c=0.51, EtOH)

Odour description: fruity, spicy, woody

EXAMPLE 7 5-Isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-ol (7A and7B)

At 5° C., a soln. of 1 g of5-isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-one (4.9 mmol) in 5ml ethanol was treated with 0.37 g NaBH₄ (9.8 mmol, 2 eq.). The reactionmixture was then stirred 2 h at 25° C., poured into 1N aq. HCl soln.,and extracted with Et₂O. The org. phase was washed with aq. sat. NaClsoln., dried, and concentrated. FC (hexane/Et₂O 9:1 to 9:2) of the crude(1 g, 7A/7B 30:70) gave 0.1 g 7A (10%), 0.2 g 7A/7B (1:1, 20%), and 0.4g 7B (40%).

(1S*2R*4S*5R*)-5-Isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-ol (7A(exo))

Boiling point: 100° C. at 0.06 torr (0.08 mbar).

¹H-NMR (400 MHz, CDCl₃): δ5.44 (tq, J=1.4, 3.5, H—C(7)), 4.67-4.64 (m,C═CH₂), 3.90 (dt, J=2.8, 2.9, H—C(2)), 2.29-2.25 (m, H—C(1)), 2.20 (dd,J=3.0, 12.6, H_(syn)—C(9)), 2.10-2.05 (m, C(6)H₂), 2.02 (ddd, J=3.7,6.2, 14.9, H_(α)—C(3)), 1.82-1.75 (m, H—C(4)), 1.69 (td, J=1.6, 2.1,MeC(8)), 1.66 (dd, J=0.6, 1.1, MeC═CH₂), 1.45 (ddt, J=1.6, 1.8, 14.8,H_(β)—C(3)), 1.37 (ddd, J=1.2, 1.7, 12.6, H_(anti)—C(9)), 0.98 (d,J=7.3, MeC(4)).

¹³C-NMR (100 MHz, CDCl₃): δ152.93 (s, C(5)C═), 135.27 (s, C(8)), 123.66(d, C(7)), 107.21 (t, CH₂—), 68.41 (d, C(2)), 43.39 (d), 39.36 (t,C(6)), 39.18 (s, C(5)), 35.96 (d), 32.99 (t, C(9)), 24.12 (t, C(3)),22.26 (q, MeC(8)), 18.87 (q, MeC═CH₂), 17.91 (q, MeC(4)).

MS (EI): 206 (17), 188 (44), 173 (32), 159 (14), 147 (19), 145 (26), 133(58), 119 (66), 107 (71), 105 (77), 93 (100), 77 (50), 71 (24), 55 (36),41 (70).

[α]_(D) ²²=−141.4 (c=0.89, EtOH)

Odour description: floral, agrestic, rosy, green

(1S*2S*4S*5R*)-5-Isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-ol(7B(endo))

Boiling point: 80° C. at 0.05 torr (0.07 mbar).

¹H-NMR (400 MHz, CDCl₃): δ5.60 (tq, J=1.5, 3.5, H—C(7)), 4.63 (quintet,J=1.4, H_(t)—CH═), 4.58-4.56 (br. s, H_(c)—CH═), 4.03 (dt, J=4.4, 11.5,irrad. at 2.48→dd, J≈4.4, 11.2, H—C(2)), 2.50-2.45 (m, irrad. at4.03→changes, H—C(1)), 2.12-2.00 (br. s, C(6)H₂), 1.89 (br. quintet t,J=1.7, 7.1, H—C(4)), 1.86-1.76 (m, irrad. at 4.03→changes, irrad. at2.48→changes, H_(syn)—C(9)), H_(α)—C(3)), 1.81 (td, J=1.6, 2.2, MeC(8)),1.64 (br. d, J=0.8, MeC═CH₂), 1.57 (ddd, J=1.8, 3.7, 12.8, irrad. at2.48→dd, J≈2.0, 12.8, H_(anti)—C(9)), 1.55 (dddd, J=1.4, 1.8, 4.4, 12.4,irrad. at 4.03→dt, J≈1.9, 11.6, irrad. at 2.48→dd, J=2.0, 4.4, 12.4,H_(β)—C(3)), 1.33-1.21 (br. s, OH), 0.80 (d, J=7.2, MeC(4)).

¹H-NMR (400 MHz, C₆D₆): δ5.52 (tq, J=1.5, 3.4, H—C(7)), 4.68 (quintet,J=1.4, H_(t)—CH═), 4.63-4.61 (br. s, H_(c)—CH═), 3.73 (dt, J=4.4, 11.6,H—C(2)), 2.29-2.25 (m, H—C(1)), 2.03-1.95 (m, H—C(6)), 1.91 (td, J=1.6,2.1, MeC(8)), 1.88-1.80 (m, H—C(6)), 1.77 (td, J=5.3, 12.2, H_(α)—C(3)),1.61 (br. quintet t, J=1.8, 7.2, H—C(4)), 1.62-1.57 (m, H_(syn)—C(9)),1.52 (dd, J=0.6, 1.3, MeC═CH₂), 1.49 (ddd, J=1.8, 3.7, 12.7H_(anti)—C(9)), 1.30 (dddd, J=1.3, 2.0, 4.4, 12.6, H_(β)—C(3)), 0.71 (d,J=7.2, MeC(4)), 0.66-0.57 (br. s, OH).

¹³C-NMR (100 MHz, CDCl₃): δ152.26 (s, C(5)C═), 133.63 (s, C(8)), 124.24d, C(7)), 107.48 (t, CH₂═), 69.53 (d, C(2)), 42.84 (d), 39.94 (t, C(6)),38.64 (s, C(5)), 37.23 (d), 34.61 (t, C(9)), 29.57 (t, C(3)), 25.05 (q,MeC(8)), 18.26 (q, MeC═CH₂), 16.15 (q, MeC(4)).

MS (EI): 206 (17), 188 (44), 173 (32), 159 (14), 147 (19), 145 (26), 133(58), 119 (66), 107 (71), 105 (77), 93 (100), 77 (50), 71 (24), 55 (36),41 (70).

IR: ν_(max) 3282, 2966, 2933, 2880, 1637, 1443, 1375, 1355, 1329, 1296,1250, 1162, 1079, 1047, 1029, 998, 887, 821, 792, 632 cm⁻¹.

[α]_(D) ²²=−226.0 (c=0.98, EtOH)

Odour description: floral, isononanol-like, grapefruit

EXAMPLE 8 5-Isopropenyl-2,4,8-trimethylbicyclo[3.3.1]non-7-en-2-ol (8Aand 8B)

At 5° C., a soln. of 1 g of5-isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-one (4.9 mmol) in 15ml THF was treated dropwise with 21 ml 1.4M MeLi in Et₂O (29.4 mmol, 6eq.). The reaction mixture was stirred 5 h at 5° C., warmed to 25° C.overnight, poured into aq. sat. NH₄Cl soln., and extracted with Et₂O.The org. phase was washed with aq. sat. NaCl soln., dried, andconcentrated. FC (SiO₂, hexane/Et₂O 9:1) of the crude (1.2 g, startingmaterial/OH exo/OH endo 17:65:18)gave 0.2 g of starting material (20%),0.5 g 8A (46%), 0.25 g 8A/8B (1:1, 23%), and 0.1 g 8B (9%).

(1S*2R*4S*5R*)-5-Isopropenyl-2,4,8-trimethylbicyclo[3.3.1]non-7-en-2-ol(8A(exo))

Boiling point: 80° C. at 0.07 torr (0.09 mbar)

¹H-NMR (400 MHz, CDCl₃): δ5.44 (tq, J=1.5, 3.7, H—C(7)), 4.66-4.64 (br.s, H_(c)—CH═), 4.63 (quintet, J=1.4, H_(t)—CH═), 2.26 (dd, J=3.1, 12.5,H_(syn)—C(9)), 2.10-2.05 (m, C(6)H₂, H—C(1)), 1.92 (dd, J=6.1, 14.4,H_(α)—C(3)), 1.81 (quintet t, J=1.5, 7.2, H—C(4)), 1.77 (td, J=1.5, 2.2,MeC(8)), 1.67 (dd, J=0.6, 1.3, MeC═CH₂), 1.38 (ddd, J=1.5, 3.0, 12.5,H_(anti)—C(9)), 1.31 (dt, J=1.6, 14.4, H_(β)—C(3)), 1.27-1.21 (br. s,OH), 1.18 (s, MeC(2)), 0.98 (d, J=7.3, MeC(4)).

¹³C-NMR (100 MHz, CDCl₃): δ152.70 (s, C(5)C═), 135.83 (s, C(8)), 124.48(d, C(7)), 107.11 (t, CH₂═), 73.24 (s, C(2)), 47.84 (d, C(1)), 39.91 (t,C(6)), 38.86 (s, C(5)), 38.49 (t), 36.85 (d, C(4)), 31.31 (q, MeC(2)),26.92 (t), 24.57 (q, MeC(8)), 18.06, 18.03 (2q, MeC═CH₂, MeC(4)).

MS (EI): 220 (6), 202 (22), 187 (18), 162 (48), 147 (21), 135 (56), 119(55), 107 (66), 93 (74), 85 (100), 77 (39), 67 (26), 55 (28), 43 (81).

IR: ν_(max) 3417, 2968, 2928, 2833, 1640, 1446, 1372, 1329, 1302, 1210,1151, 1121, 1104, 1033, 942, 926, 886, 832, 800, 781 cm⁻¹.

Odour description: fruity, agrestic, rosy, earthy

(1S*2S*4S*5R*)-5-Isopropenyl-2,4,8-trimethylbicyclo[3.3.1]non-7-en-2-ol(8B(endo))

Boiling point: 60° C. at 0.06 torr (0.08 mbar).

¹H-NMR (400 MHz, CDCl₃): δ5.56 (tq, J=1.6, 3.5, H—C(7)), 4.62 (quintet,J=1.4, H_(r)—CH═), 4.60-4.58 (br. s, H_(c)—CH═), 2.18-2.14 (m, H—C(1)),2.13-2.08 (m, C(6)H₂), 1.97 dd, J=6.3, 13.1, H_(α)—C(3)), 1.90 (quintett, J=1.5, 7.2, H—C(4)), 1.86 (dd, J=3.0, 13.1, H_(syn)—C(9)), 1.84 (td,J=1.5, 2.2, MeC(8)), 1.54 (ddd, J=1.8, 3.5, 13.1, H_(anti)—C(9)), 1.42(dt, J=1.4, 13.0, H_(β)—C(3)), 1.41-1.39 (br. s, MeC═CH₂), 1.32-1.22(br. s, OH), 1.26 (s, MeC(2)), 0.83 (d, J=7.5, MeC(4)).

¹³C-NMR (100 MHz, CDCl₃): δ152.13 (s, C(5)C═), 135.70 (s, C(8)), 124.14(d, C(7)), 107.24 (t, CH₂═), 73.32 (s, C(2)), 47.42 (d, C(1)), 40.90,40.27 (2t, C(3), C(6)), 38.71 (s, C(5)), 37.23 (d, C(4)), 29.24 (t),29.02 (q, MeC(2)), 25.46 (q, MeC(8)), 18.18, 17.49 (2q, MeC═CH₂, MeC(4).

MS (EI): 220 (4), 202 (24), 187 (16), 162 (46), 147 (22), 135 (56), 119(55), 107 (66), 93 (74), 85 (100), 77 (39), 67 (26), 55 (28), 43 (81).

IR: ν_(max) 3452, 2924, 2881, 1638, 1448, 1376, 1289, 1258, 1160, 1140,1109, 1061, 1019, 943, 931, 907, 887, 829, 800, 656 cm⁻¹.

Odour description: fruity, rosy

EXAMPLE 9 5-Isopropyl-4,8-dimethylbicyclo[3.3.1]nonan-2-one (9)

At 25° C., a mixture of 1 g5-isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-one (4.9 mmol) and 50mg 10% Pd/C in 10 ml MeOH was stirred under 10 bar of H₂ for 5 h.Filtration (Celite®), concentration, and FC (SiO₂, hexane/Et₂O 100:7)gave 0.22 g (22%) of compound 9. The boiling point of the end product is75° C. at 0.07 torr (0.09 mbar).

¹H-NMR (400 MHz, CDCl₃): δ2.69 (dd, J=8.2, 17.4, H_(α)—C(3)), 2.38-2.31(br. s, H—C(1)), 2.20 (br. d, J=17.1, H_(β)—C(3)), 2.23-2.12 (m, 1H),1.79-1.38 (m, 8H), 0.93 (d, J=7.1, Me), 0.88 (d, J=6.8, Me), 0.84 (d,J=6.2, Me), 0.82 (d, J=6.5, Me).

¹H-NMR (400 MHz, C₆D₆): δ2.39 (dd, J=8.1, 17.2, H_(α)—C(3)), 2.31-2.26(m, H—C(1)), 2.12 (br. d, J=17.3, H_(β)—C(3)), 1.73 (br. quintet, J=7.1,H—C(4)), 1.53-1.41 (m, H_(anti)—C(9), H—C(7)), 1.40-1.30 (m, H—C(6),H—C(8), CHMe₂), 1.29 (dt, J=2.3, 13.5, H_(anti)—C(9)), 1.23-1.10 (m,H—C(7), H—C(6)), 0.62 (d, J=6.7, MeC(8)), 0.69 (d, J=6.8, MeCHMe), 0.68(d, J=7.2, MeC(4)), 0.62 (d, J=6.9, MeCHMe).

¹³C-NMR (100 MHz, CDCl₃): δ214.61 (s, CO), 52.70 (d), 49.67 (t), 37.65(d), 35.51 (s), 34.33 (d), 33.36 (t), 32.98 (d), 29.93 (t), 28.19 (t),19.86 (q), 18.34 (q), 17.11 (q), 15.84 (q).

¹³C-NMR (100 MHz, C₆D₆): δ210.00 (s, CO), 52.88 (d, C(1)), 49.86 (t,C(3)), 37.68 (d, C(4)), 35.72 (s, C(5)), 34.50 (d, C(8)), 33.51 (t,C(9)), 33.17 (d, CHMe₂), 30.25 (t, C(7)), 28.44 (t, C(6)), 20.23 (q,Me—C(8)), 18.38 (q, Me—C(4)), 17.28, 16.03 (2q, Me₂C).

MS (EI): 208 (22), 193 (7), 190 (3), 165 (36), 147 (14), 137 (58), 123(24), 109 (15), 95 (84), 81 (100), 67 (30), 55 (36), 41 (45).

[α]_(D) ²²=−108.8 (c=1.06, EtOH).

Odour description: fruity, agrestic, rosy, woody

EXAMPLE 10 (1S*5R*)-5-Isopropenyl-8-methylbicyclo[3.3.1]non-7-en-2-one(10)

A mixture of 20.0 g acryloyl chloride (0.22 mol) and 3.01 g zincchloride (0.02 ml, 0.1 eq.) in 150 ml ethylene chloride was treated witha soln. of 350 ml α-pinene ((1S-(−)/(1R)-(+) 90:10, 2.20 mol, 10 eq.) in250 ml ethylene chloride and the resulting mixture was stirred 1 h at25° C. and 4 h at 50° C. After cooling, the reaction mixture was washedwith aq. sat. NaCl soln. and aq. sat. NaHCO₃ soln. The aq. phases wereextracted with Et₂O, dried (Na₂SO₄), and concentrated. The crude product(48 g) was filtered (SiO₂, hexane/Et₂O 200:6→200:10) and the residue(1.42 g) treated with 300 mg LiOH.H₂O in 15 ml MeOH at 25° C. for 7 h.The resulting mixture was poured into aq. sat. NaCl soln., extractedwith hexane and the org. phases dried with Na₂SO₄, FC (SiO₂, hexane/Et₂O30:1) gave 347 mg (0.8%) of compound 10. Boiling point: 80° C. at 0.07torr (0.09 mbar).

¹H-NMR (400 MHz, CDCl₃): δ5.65 (tq, J=1.5, 3.3, H—C(7)), 4.5-4.743 (br.s, H_(c)—CH═), 4.72 (quintet, J=1.4, H_(t)—CH═), 2.85 (br. t, J=3.1,H—C(1)), 2.79 (ddd, J=6.8, 13.7, 15.4, H_(α)—C(3)), 2.375 (br. d,J=18.8, H—C(6)), 2.295 (dddd, J=1.9, 3.9, 5.8, 18.9, H—C(6)), 2.12(dddd, J=1.3, 2.2, 5.9, 15.3, H_(β)—C(3)), 2.13-2.06 (m, H_(α)—C(4)),2.03-2.00 (br. s, C(9)H₂), 1.78 (dd, J=0.7, 1.3, MeC═CH₂), 1.73 (dddd,J=1.5, 6.0, 13.4, H—C_(β)(4)), 1.67 (dt, J=1.6, 2.2, MeC(8)).

¹³C-NMR (100 MHz, CDCl₃): δ212.05 (s, CO), 152.28 (s, C(5)C═), 133.76(s, C(8)), 125.20 (d, C(7)), 108.06 (t, CH₂═), 53.65 (d, C(1)), 38.13(t), 36.68 (t), 36.00 (s, C(5)), 35.64 (t), 34.25 (t), 21.99 (q,MeC(8)), 19.06 (q, MeC═CH₂).

MS (EI): 190 (16), 175 (5), 162 (1), 157 (4), 147 (9), 133 (27), 119(28), 105 (58), 98 (21), 93 (100), 91 (65), 83 (95), 77 (37), 65 (17),55 (20), 41 (42).

IR: ν_(max) 2929, 1737, 1712, 1637, 1443, 1379, 1241, 1151, 1119, 1058,993, 890, 789 cm⁻¹.

[α]_(D) ²²=−55.0 (c=0.79, EtOH)

Odour description: woody (pine, cedarwood), ambery, sweet

EXAMPLE 11(1S*3R*4S*5R*)-5-Isopropenyl-3,4,8-trimethylbicyclo[3.3.1]non-7-en-2-one(11)

Method a) A mixture of 11.81 g 2-methyl-but-2-enoyl chloride (0.10 mol)and 1.36 g zinc chloride (0.01 mol, 0.1 eq.) in 100 ml ethylene chloridewas treated with a soln. of 136 g α-pinene ((1S)-(−)/(1R)-(+) 90:10, 1mol, 10 eq.) in 150 ml ethylene chloride and the resulting mixture wasstirred 45 min. at 25° C., 2.5 h at 50° C., and 1 h at 80°. Aftercooling, the reaction mixture was washed with aq. sat. NaCl soln. andaq. sat. NaHCO₃ soln. The aq. phases were extracted with Et₂O, dried(Na₂SO₄), and concentrated. The crude product (48 g) filtered (SiO₂,hexane/Et₂O 200:6→200:13) and the residue (5.1 g) treated with 1 gLiOH.H₂O in 75 ml MeOH at 25° C. for 48 h. The resulting mixture waspoured into aq. sat. NaCl soln. and extracted with hexane. The combinedorg. phases were dried (Na₂SO₄), concentrated and purified by FC (SiO₂,hexane/Et₂O 100:3) gave 1.6 g (7.1%) of compound 11.

Method b) 15 ml of a soln. of 0.116 M of EtONa in EtOH were treated with1.5 g of 5-isopropenyl-3,4,8-trimethylbicyclo[3.3.1]non-7-en-2-one andheated 4 h at reflux. The resulting mixture was poured into 50 ml 2M aq.HCl and extracted with 2×50 ml MTBE. The org. phases were washed with 50ml H₂O, 50 ml aq. sat. NaCl soln., and dried. FC (SiO₂, hexane/MTBE20:1) gave 0.75 g (50%) of compound 11. Boiling point: 80° C. at 0.08mbar.

¹H-NMR (400 MHz, CDCl₃): δ5.61 (tq, J=1.5, 3.2, H—C(7)), 4.73 (quintet,J=1.3, H_(r)—CH═), 4.64-4.62 (br. s, H_(c)—CH═), 3.26 (qd, J=5.8, 6.7,H—C(3)), 2.83 (br. t, J=3.1, H—C(1)), 2.45-2.33 (m, C(6)H₂), 2.13 (qqq,J=2.5, 5.6, 7.0, H—C(4)), 2.11 (dd, J=3.4, 12.6, H_(syn)—C(9)), 1.85(dt, J=2.7, 12.6, H_(anti)—C(9)), 1.72 (dd, J=0.8, 1.2, MeC═CH₂), 1.66(dt, J=1.6, 2.3, MeC(8)), 0.93 (d, J=6.7, MeC(3)), 0.63 (d, J=7.1,MeC(4)).

¹³C-NMR (100 MHz, CDCl₃): δ214.66 (s, CO), 151.19 (s, C(5)C═), 135.89(s, C(8)), 124.96 (d, C(7)), 108.94 (t, CH₂═), 54.02 (d, C(1)), 46.01(t, C(3)), 40.96 (s, C(5)), 39.47 (t, C(6)), 39.30 (d, C(4)), 32.16 (t,C(9)), 22.21 (q, MeC(8)), 18.63 (q, MeC═CH₂), 12.38, 10.51 (2q, MeC(3),MeC(4)).

MS (EI): 218 (27), 203 (7), 190 (8), 175 (9), 161 (12), 147 (17), 133(59), 119 (100), 105 (75), 95 (13), 93 (67), 91 (85), 77 (52), 69 (7),55 (65), 41 (65).

IR: ν_(max) 2968, 2927, 1708, 1677, 1638, 1446, 1381, 1351, 1238, 1210,1152, 1103, 1083, 1059, 1003, 869, 830, 802, 790, 659 cm⁻¹.

[α]_(D) ²²=−768.6 (c=0.97, EtOH)

Odour description: fruity, peppery, woody, elemi, gurjun, ambery

EXAMPLE 12 4,8-Dimethyl-5-isopropenyl-8-methoxy-bicyclo[3.3.1]non-7-ene(12A and 12B)

A soln. of 2.9 g of5-isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-ol (14.1 mmol, α/β58:42) in 30 ml DMF was added dropwise to a suspension of 0.84 g 55-65%sodium hydride (21 mmol, 1.5 eq.) in 30 ml DMF and the resulting mixturewas stirred 1.5 h at 25° C., treated with 2.6 ml methyl iodide (41.8mmol, 3 eq.), heated 4.5 h at 80° C., poured into 50 ml HCl 2M, andextracted with 2×80 ml hexane. The org. phases were washed with 2×100 ml1:1 aq. sat. NaCl soln./H₂O, dried, and concentrated. FC (hexane/MTBE15:1) of the crude (2.17 g) gave 0.25 g 12A (8.1%), 0.85 g 12B/12A(55:45, 27.4%), and 1.07 g 12B (34.5%).

(1S*2R*4S*5R*)-4,8-Dimethyl-5-isopropenyl-8-methoxy-bicyclo[3.3.1]non-7-ene(12A)

Boiling point: 80° C. at 0.08 mbar.

¹H-NMR (400 MHz, CDCl₃): δ5.46 (tq, J=1.4, 3.2, H—C(7)), 4.64-4.62 (m,C═CH₂), 3.33 (s, MeO), 3.29 (dt, J=2.8, 2.9, H—C(2)), 2.41-2.37 (br. s,H—C(1)), 2.11 (dd, J=3.0, 12.5, H_(syn)—C(9)), 2.08-2.05 (m, C(6)H₂),1.81 (ddd, J=3.6, 5.8, 14.6, H_(α)—C(3)), 1.74 (br. quintet, J=7.0,H—C(4)), 1.69 (td, J=1.6, 2.1, MeC(8)), 1.65 (br. t, J=0.9, MeC═CH₂),1.63 (ddt, J=1.5, 1.8, 15.0, ,H_(β)—C(3)), 1.33 (br. d, J=12.5,H_(anti)—C(9)), 0.91 (d, J=7.2, MeC(4)).

¹³C-NMR (100 MHz, CDCl₃): δ153.16 (s, C(5)C═), 135.24 (s, C(8)), 124.13(d, C(7)), 107.26 (t, CH₂═), 77.51 (d, C(2)), 56.11 (q, MeO), 40.59 (d),39.54 (t, C(6)), 39.26 (s, C(5)), 36.46 (d), 28.29 (t, C(9)), 24.85 (t,C(3)), 22.34 (q, MeC(8)), 18.06 (q, MeC═CH₂), 17.92 (q, MeC(4)).

MS (EI): 220 (4), 205 (1), 188 (18), 173 (10), 159 (3), 145 (8), 133(34), 119 (17), 107 (17), 105 (32), 93 (24), 91 (32), 85 (100), 77 (20),71 (6), 55 (19), 41 (26).

IR: ν_(max) 2962, 2925, 2889, 2826, 1638, 1447, 1375, 1193, 1160, 1118,1108, 1097, 1081, 970, 959, 924, 886, 829, 804, 786 cm⁻¹.

[α]_(D) ²²=−90.8 (c=0.14, EtOH)

Odour description: woody, ambery

(1S*2S*4S*5R*)-4,8-Dimethyl-5-isopropenyl-8-methoxy-bicyclo[3.3.1]non-7-ene(12B)

Boiling point: 80° C. at 0.08 mbar.

¹H-NMR (400 MHz, CDCl₃): δ5.55 (tq, J=1.6, 3.2, H—C(7)), 4.62 (quintet,J=1.4 H_(r)—CH═), 4.57-4.56 (br. s, H_(C)—CH═), 3.49 (dt, J=4.2, 11.6,H—C(2)), 3.36 (s, MeO), 2.66-2.62 (br. s, H—C(1)), 2.10-2.00 (m,C(6)H₂), 1.95-1.85 (br. quintet, J=7.1, H—C(4)), 1.81 (td, J=5.4, 12.2,H_(α)—C(3)), 1.76 (dt, J=1.6, 2.2, MeC(8)), 1.74 (dd, J≈2.8, 13.0,H_(syn)—C(9)), 1.64 (dd, J=0.5, 1.3, MeC═CH₂), 1.59 (ddd, J=1.8, 3.9,12.8, H_(anti)—C(9)), 1.56 (dddd, J=1.4, 2.0, 4.2, 12.6, H_(β)—C(3)),0.79 (d, J=7.2, MeC(4)).

¹³C-NMR (100 MHz, CDCl₃): δ152.58 (s, C(5)C═), 134.29 (s, C(8)), 123.66(d, C(7)), 107.46 (t, CH₂═), 78.58 (d, C(2)), 55.98 (q, MeO), 40.00 (t,C(6)), 39.06 (s, C(5)), 38.53 (d), 37.11 (d), 31.72, 29.58 (2 t, C(9),C(3)), 24.42 (q, MeC(8)), 18.35 (q, MeC═CH₂), 16.43 (q, MeC(4)).

MS (EI): 220 (5), 205 (1), 188 (19), 173 (10), 159 (3), 145 (8), 133(31), 119 (16), 107 (15), 105 (29), 93 (22), 91 (30), 85 (100), 77 (18),71 (5), 55 (18), 41 (23).

IR: ν_(max) 2965, 2935, 2890, 2828, 1638, 1451, 1374, 1194, 1176, 1103,1040, 1011, 975, 945, 923, 887, 820, 793, 625 cm⁻¹.

[α]_(D) ²²=−195.4 (c=0.76, EtOH)

Odour description: woody, ambery, fatty, green

EXAMPLE 13 A Fragrance Composition of Shower Gel

compound/ingredient parts by weight 1/1000 Armoise oil  5 Grisalva(5,5,9-Trimethyl-1-  5 ethyltricyclo[8.4.0.0-4,9]-14-oxatetradecane)Clary sage oil 10 Jasmonyl (1,3-Nonanediol acetate) 10 Limette oil 10Patchouli oil 10 Piconia (Isolongifolanone) 10 Verbena oil Africa 10Oakmoss absolute Tyrol at 50% in DPG 20 Geranium oil 25 Rosemary oil 25Sandela (3-Isocamphylcyclohexanol) 25 Lavandin Grosso oil 30 Cinnamonleaves oil 30 Juniper oil 30 Methyl cedryl ketone 30 Dimyrcetol 40Fixolide (7-Acetyl-1,1,3,4,4,6-hexamethyltetralin) 40 Lilial(p-tert.Butyl-alpha-methyldihydrocinnamic 40 aldehyde) Neroli essentialoil 45 Bornyl acetate 50 Cedryl acetate 50 Para-tert-butylcyclohexylacetate 50 Hydroxy citronellal 50 Irisantheme (alpha-Isomethylionone) 50Linalyl acetate 65 Galaxolide 50% Benzyl benzoate 65 Lemon oil Italy 70Bergamot oil 90 5-Isopropenyl-4,8-dimethylbicyclo[3.3.1]non- 107-en-2-one (1) 1000 Adding 5-Isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-one (1) to thefragrance composition adds a sophisticated woody-ambery note with fruity(raspberry) undertones. It also imparts more volume to the woody accordin a fir balsam direction.

1. A compound of formula (I)

wherein R is isopropyl or iso-propenyl; R¹ is hydrogen, methyl or ethyl;R² and R³ are independently hydrogen, methyl, or ethyl; or R² and R³taken together is ethylidene; or R² and R³ taken together is a divalentradical (CH₂)₂ which forms cyclopropane together with the carbon atom towhich they are attached; R⁴ and R⁵ are independently hydrogen, hydroxy,C₁ to C₃ alkoxy, or C₂ to C₃ acyloxy; or R⁴ and R⁵ together with thecarbon atom to which they are attached form a 1,3-dioxolane ring or a1,3-dioxane ring; or R⁴ and R⁵ together with the carbon atom to whichthey are attached form a carbonyl group; the bond between C2 and C3 is asingle bond, or the dotted line together with the bond between C2 and C3represents a double bond; and the bond between C7 and C8 is a singlebond, or the dotted line together with the bond between C7 and C8represents a double bond.
 2. A flavour or fragrance compositioncomprising a compound of formula (I) as defined in claim
 1. 3. A flavouror fragrance ingredient comprising a compound of formula (I) as definedin claim
 1. 4. A method of manufacturing a flavour or fragrancecomposition, comprising the step of incorporating a compound of formula(I) as defined in claim 1 to a base material.
 5. A method ofmanufacturing a fragranced application, comprising the incorporation ofa compound of formula (I) as defined in claim
 1. 6. A method accordingto claim 5 wherein the fragranced application is selected from the groupconsisting of perfume, household product, laundry product, body careproduct and cosmetics.
 7. A compound according to claim 1 selected fromthe group consisting of:5-isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-one;4-ethyl-5-isopropenyl-8-methylbicyclo[3.3.1]non-7-en-2-one;5-isopropenyl-3,4,8-trimethylbicyclo[3.3.1]non-7-en-2-one;5-isopropenyl-3,3,4,8-tetramethylbicyclo[3.3.1]non-7-en-2-one;5-isopropenyl-8,8-dimethoxy-2,6-dimethylbicyclo[3.3.1]non-2-ene;4,8-dimethyl-5-isopropenylspiro[bicyclo[3.3.1]nonane-2,2′-[1,3]dioxolane];5-isopropenyl-4,8-dimethylbicyclo[3.3.1]non-7-en-2-ol;5-isopropenyl-2,4,8-trimethylbicyclo[3.3.1]non-7-en-2-ol;5-isopropyl-4,8-dimethylbicyclo[3.3.1]nonan-2-one,5-isopropenyl-8-methylbicyclo[3.3.1]non-7-en-2-one,5-isopropenyl-3,4,8-trimethylbicyclo[3.3.1]non-7-en-2-one, and4,8-dimethyl-5-isopropenyl-8-methoxy-bicyclo[3.3.1]non-7-ene.
 8. Aflavour or fragrance ingredient comprising a compound of formula (I) asdefined in claim
 7. 9. A method of manufacturing a flavour or fragrancecomposition, comprising the step of incorporating a compound of formula(I) as defined in claim 7 to a base material.
 10. A method ofmanufacturing a fragranced application, comprising the incorporation ofa compound of formula (I) as defined in claim
 7. 11. A method accordingto claim 10 wherein the fragranced application is selected from thegroup consisting of perfume, household product, laundry product, bodycare product and cosmetics.